Method of manufacturing 1-chloro-2,3,3-trifluoropropene

ABSTRACT

There is provided a method of efficiently manufacturing 1-chloro-2,3,3-trifluoropropene by an industrially feasible method by using a raw material which is easy to obtain. A method of manufacturing 1-chloro-2,3,3-trifluoropropene, including subjecting 3-chloro-1,1,2,2-tetrafluoropropane to a dehydrofluorination reaction in the presence of a base.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 15/881,171 filed Jan. 26, 2018, which is acontinuation of prior International Application No. PCT/JP2016/071877,filed on Jul. 26, 2016 which is based upon and claims the benefit ofpriority from Japanese Patent Application No. 2015-148070, filed on Jul.27, 2015; the entire contents of all of which are incorporated herein byreference.

FIELD

The present invention relates to a method of manufacturing1-chloro-2,3,3-trifluoropropene.

BACKGROUND

1-chloro-2,3,3-trifluoropropene (CHCl═CF—CHF₂. HCFO-1233 yd.hereinafter, also mentioned as 1233 yd.) is a compound which issubstituted for 3,3-dichloro-1,1,1,2,2-pentafluoropropane(CF₃—CF₂—CHCl₂, HCFC-225ca) and1,3-dichloro-1,1,2,2,3-pentafluoropropane (CClF₂—CF₂—CClFH, HCFC-225cb)and used for new cleaning agent, refrigerant, foaming agent, solvent,and aerosol applications which have a small global warming potential(GWP).

In this description, regarding halogenated hydrocarbon, an abbreviatedname of the compound is mentioned in parentheses behind a compound name,and the abbreviated name is used instead of the compound name asnecessary in this description.

In 1233 yd, a Z-isomer and an E-isomer which are geometric isomers existaccording to positions of substituents on a double bond. When thecompound name or the abbreviated name of the compound is used unlessotherwise stated in this description, at least one type selected fromthe Z-isomer and the E-isomer is indicated, and when (E) or (Z) isdenoted behind the compound name or the abbreviated name of thecompound, an (E)-isomer or a (Z)-isomer of each compound is indicated.For example, HCFO-1233 yd(Z) indicates the Z-isomer, and HCFO-1233 yd(E)indicates the E-isomer.

As a manufacturing example of 1233 yd, an example in Patent Reference 1(International Publication WO 1994/14737) mentions that when3-chloro-1,1,2,2-tetrafluoropropane (CHF₂—CF₂—CH₂Cl. HCFC-244 ca.hereinafter, also mentioned as 244 ca.) and hydrogen fluoride are eachintroduced in a gas state under a nitrogen gas stream into a reactiontube made of HASTELLOY C and filled with a chromium hydroxide catalyst,a small amount of 1233 yd is by-produced with1,1,2,2,3-pentafluoropropane (CHF₂—CF₂—CH₂F, HCFC-245ca).

However, the reaction mentioned in Patent Reference 1 is not suitablefor mass production on an industrial scale because a conversion ratio ofthe raw materials is about 70%, and a production amount of 1233 yd is aby-production amount and a very small amount.

The present inventors have considered a de-HX reaction (where, X informulas indicates Cl, I, or Br) in which a compound represented by thefollowing formula (A) or a compound represented by the following formula(B) is used as a raw material, as another possibility of manufacturing1233 yd.

However, either of these compounds is not an easily obtainable compound,and there is not a method of industrially easily manufacturing themeither, so that they are difficult to obtain. In addition, in a compound(CHF₂—CHF—CHFCl, HCFC-244ea) in which X is F in the formula (B), adehydrochlorination reaction has priority over the de-HX reaction, andtherefore 1233 yd cannot be selectively obtained.

SUMMARY

In the present invention, it is an object thereof to provide aneconomically advantageous method of efficiently manufacturing 1233 yd byan industrially feasible method by using a raw material which is easy toobtain.

The present inventors have eagerly studied a method in which as aprecursor when 1233 yd is manufactured, 244 ca in which a stablemanufacturing method is established is selected and 1233 yd ismanufactured by subjecting the 244 ca to a dehydrofluorination reaction.As a result, they have found that employing not a gas phase reactionusing activated carbon, a metal catalyst, or the like which is employedas a condition of a normal dehydrofluorination reaction but a reactionusing a base makes it possible to manufacture 1233 yd selectively, andhave completed the present invention.

That is, in the present invention, a method of manufacturing 1233 yd,which has the constitution indicated below, is provided.

[1] A method of manufacturing 1-chloro-2,3,3-trifluoropropene (1233 yd),the method including subjecting 3-chloro-1,1,2,2-tetrafluoropropane (244ca) to a dehydrofluorination reaction in a presence of a base.

[2] The method of manufacturing 1233 yd according to [1], wherein thebase is at least one selected from a group consisting of a metalhydroxide, a metal oxide, and a metal carbonate.

[3] The method of manufacturing 1233 yd according to [1], wherein thebase is a metal hydroxide.

[4] The method of manufacturing 1233 yd according to [1], wherein thebase is at least one selected from a group consisting of potassiumhydroxide and sodium hydroxide.

[5] The method of manufacturing 1233 yd according to any one of [1] to[4], wherein an amount of the base is 0.5 to 10.0 mol with respect to 1mol of the 244 ca. [6] The method of manufacturing 1233 yd according toany one of [1] to [5], wherein the dehydrofluorination reaction isperformed at a reaction temperature of 5 to 80° C.

[7] The method of manufacturing 1233 yd according to any one of [1] to[6], wherein the 244 ca is subjected to a dehydrofluorination reactionin a liquid phase in a presence of a solvent and the base.

[8] The method of manufacturing 1233 yd according to [7], wherein thesolvent is water. [9] The method of manufacturing 1233 yd according to[7] or [8], wherein an amount of the base is 0.5 mass % to 48 mass %with respect to total mass of the solvent and the base.

[10] The method of manufacturing 1233 yd according to any one of [7] to[9], wherein the dehydrofluorination reaction is performed in a presenceof a phase-transfer catalyst.

[11] The method of manufacturing 1233 yd according to [10], wherein thephase-transfer catalyst is a quaternary ammonium salt.

[12] The method of manufacturing 1233 yd according to [11], wherein thequaternary ammonium salt is at least one selected from a groupconsisting of tetra-n-butylammonium chloride, tetra-n-butylammoniumbromide, and methyltri-n-octylammonium chloride.

[13] The method of manufacturing 1233 yd according to any one of [7] to[9], wherein the dehydrofluorination reaction is performed in a presenceof a water-soluble organic solvent capable of dissolving the 244 ca.

[14] The method of manufacturing 1233 yd according to [13], wherein thewater-soluble organic solvent is used in a proportion of 1 to 200 partsby mass to 100 parts by mass of the 244 ca.

A method of manufacturing 1233 yd of the present invention is a methodof using 244 ca in which a stable manufacturing method is establishedand which is easy to obtain, and therefore it is a method which is easyto industrially perform and stably feasible. Further, according to themethod of manufacturing 1233 yd of the present invention, it is possibleto manufacture 1233 yd at a high reaction rate and with a highselectivity.

MODE FOR CARRYING OUT THE INVENTION

A method of manufacturing 1233 yd of the present invention ischaracterized by subjecting 244 ca to a dehydrofluorination reaction inthe presence of a base. The dehydrofluorination reaction of 244 ca(hereinafter, simply also referred to as “dehydrofluorinationreaction”.) according to the manufacturing method of the presentinvention is a reaction indicated by the following formula (1).

The dehydrofluorination reaction of 244 ca in the present invention canbe performed by either a gas phase reaction or a liquid phase reaction,and is preferably performed by the liquid phase reaction in that itsoperation is more industrially advantageous. In this description,subjecting a compound (X) to the dehydrofluorination reaction by the gasphase reaction means that the compound (X) in a gaseous state issubjected to the dehydrofluorination reaction. Subjecting the compound(X) to the dehydrofluorination reaction by the liquid phase reactionmeans that the compound (X) in a liquid state is subjected to thedehydrofluorination reaction.

In the method of manufacturing 1233 yd of the present invention, amethod of subjecting 244 ca in the liquid state to thedehydrofluorination reaction in a liquid phase is preferable from theviewpoint of a conversion ratio of 244 ca and a selectivity of 1233 yd,and the viewpoint that a size of a reactor of a reaction device can bemade smaller compared with the case of performing it in a gas phase, orthe like.

(244 ca)

In the method of manufacturing 1233 yd of the present invention, 244 cais used as a raw material. 244 ca is a compound known as a productionraw material or an intermediate of a fluorine-containing compound andcan be easily obtained.

A method of obtaining 244 ca is not particularly limited, and forexample, as indicated by a formula (2), 244 ca can be manufactured by amethod of chlorinating 2,2,3,3-tetrafluoropropanol (TFPO) with thionylchloride (SOCl₂) in the presence of N,N-dimethylformamide (DMF). Thismethod can be performed in the liquid phase or in the gas phase.

In a reaction of the formula (2), as a reactor, a commonly-used reactor,such as a glass flask, an autoclave made of SUS, and a glass-linedreactor, can be used. When the glass flask is used, it is preferable toplace a glass distillation column packed with a Raschig ring andsimultaneously perform production and separation of 244 ca.

It is preferable that an input amount of DMF is 0.001 to 0.2 mol and aninput amount of thionyl chloride is about 0.5 to 1.5 mol with respect to1 mol of TFPO. DMF has an action which acts in such a manner as to be acatalyst and makes the reaction progress. Because the reactionprogresses quantitatively in an equimolar manner in the reaction of theformula (2), both need not be excessive.

When an addition rate of thionyl chloride with respect to 1 mol of TFPOis too fast, a production rate of hydrogen chloride increases, and thereis a possibility that a product is accompanied by the hydrogen chlorideand discharged to the outside of the system to be a loss. Accordingly,thionyl chloride is preferably dropped at such a rate that a temperaturevariation due to the reaction progress falls within 30° C. Note thatwhen water exists, thionyl chloride is hydrolyzed by reacting with waterand decomposed into SO₂ and HCl. Moreover,2,2,3,3-tetrafluoropropanesulfonyl chloride is also hydrolyzed anddecomposed into TFPO, SO₂, and HCl. In order to prevent the above, anatmosphere in the reactor is preferably substituted for dry nitrogengas.

In the reaction of the formula (2), TFPO and thionyl chloride react witheach other by addition of the thionyl chloride to produce2,2,3,3-tetrafluoropropanesulfonyl chloride. Heating2,2,3,3-tetrafluoropropanesulfonyl chloride causes a de-sulfur dioxidereaction, and 244 ca is produced. A temperature at a time of the heatingis 70° C. to 150° C., and preferably 90° C. to 130° C. A temperatureincreasing rate is optional, but in order to avoid insufficienttreatment of the produced sulfur dioxide and insufficient recovery ofthe produced 244 ca, it is desirable to increase the temperature at aslow rate of about 1 to 2° C./min and regulate a production rate.

In the heating of 2,2,3,3-tetrafluoropropanesulfonyl chloride, when aregulation of the temperature increasing rate is difficult, it ispreferable to employ a method (liquid phase reaction) of heating2,2,3,3-tetrafluoropropanesulfonyl chloride in a solvent, for example.The solvent is a solvent whose boiling point is higher than the reactiontemperature in the decomposition reaction of2,2,3,3-tetrafluoropropanesulfonyl chloride and which does not easilyreact with the compounds involved in the reaction indicated by theformula (2), and an aprotic solvent is preferably used. As a specificexample, dimethyl sulfoxide, DMF, or the like can be cited. A use amountof the solvent is preferably about 0.5 to 3 mol with respect to 1 mol of2,2,3,3-tetrafluoropropanesulfonyl chloride.

A reactor similar to the one described above is prepared for thede-sulfur dioxide reaction of 2,2,3,3-tetrafluoropropanesulfonylchloride, and the reaction is preferably performed by the liquid phasereaction. That is, when the solvent is added in the reactor and heatedto a temperature at which the de-sulfur dioxide reaction is performed,244 ca is produced by dropping 2,2,3,3-tetrafluoropropanesulfonylchloride. The reaction temperature in the de-sulfur dioxide reaction is70° C. to 150° C., and preferably 90° C. to 130° C. The atmosphere inthe reactor is preferably substituted for the dry nitrogen gas.

A crude product of 244 ca produced through the reaction of the formula(2) is a gaseous crude product normally, and impurities are removed byperforming treatment which removes hydrochloric acid and sulfur dioxideby a method such as water washing, drying the product by a drying agentsuch as calcium chloride or a molecular sieve, and using a method suchas a cold trap, thereby allowing a composition including 244 ca to berecovered. The obtained composition including 244 ca can be used as itis or can be used, by purifying this further, for example, as acomposition of 244 ca with a purity of 99.5 mass % or more, for themanufacturing method of the present invention.

As 244 ca to be used for the manufacturing method of the presentinvention, other than 244 ca with a purity of 100%, the composition of244 ca with high purity which has undergone the purification process maybe used, and the composition including 244 ca which include a component(for example, an impurity or the like) other than 244 ca and 244 ca maybe used. However, in a case of using the latter composition including244 ca, when the impurity is an impurity which is activated by thereaction of the present invention, it is preferably removed in advance.For example, in a case of manufacturing 244 ca by the method of theformula (2), when TFPO remains with 244 ca to be produced, TFPOsometimes reacts with 1233 yd which is the product of the presentinvention, and therefore TFPO is preferably removed from the product asmuch as possible when used in the method of the present invention.

(Base)

In the manufacturing method of the present invention, 244 ca obtained bythe above method or the like is subjected to the dehydrofluorinationreaction in the presence of a base. The base is not particularly limitedas long as it is a base capable of carrying out the abovedehydrofluorination reaction. The base preferably includes at least onetype of base selected from a group constituted of a metal hydroxide, ametal oxide, and a metal carbonate.

When the base is the metal hydroxide, an alkaline-earth metal hydroxide,an alkali metal hydroxide, or the like can be cited. As thealkaline-earth metal hydroxide, for example, there can be citedmagnesium hydroxide, calcium hydroxide, strontium hydroxide, or bariumhydroxide. As the alkali metal hydroxide, for example, there can becited lithium hydroxide, sodium hydroxide, or potassium hydroxide.

When the base is the metal oxide, as a metal constituting the metaloxide, there can be cited alkali metal elements, alkaline-earth metalelements, transition metal elements, group 12 metal elements, or group13 metal elements. Among them, the alkali metal elements, thealkaline-earth metal elements, the group 6 metal elements, the group 8metal elements, the group 10 metal elements, the group 12 metalelements, or the group 13 metal elements are preferable, and sodium,calcium, chromium, iron, zinc, or aluminum is further preferable. Themetal oxide may be an oxide including one type of metal or may be acomposite oxide including two or more types of metals. As the metaloxide, in terms of a reaction time and a reaction yield, sodium oxide,calcium oxide, chromium oxide (chromia), aluminum oxide (alumina), zincoxide, or the like is preferable, and alumina and chromia are morepreferable.

When the base is the metal carbonate, an alkaline-earth metal carbonate,an alkali metal carbonate, or the like can be cited. As thealkaline-earth metal carbonate, for example, there can be cited acarbonate of a metal such as beryllium, magnesium, calcium, strontium,barium, or radium. As the alkali metal carbonate, for example, there canbe cited a carbonate of a metal such as lithium, sodium, potassium,rubidium, cesium, or francium.

As the base to be used for the manufacturing method of the presentinvention, in terms of the reaction time and the reaction yield, themetal hydroxide is preferable, and at least one selected from a groupconsisting of potassium hydroxide and sodium hydroxide is particularlypreferable. One type of the metal hydroxide may be used alone, or two ormore types may be used in combination.

A use amount of the base to be used for the manufacturing method of thepresent invention is preferably 0.5 to 10.0 mol, more preferably 0.5 to5.0 mol, and further preferably 0.8 to 3.0 mol with respect to 1 mol of244 ca from the viewpoint of the reaction yield and the selectivity of1233 yd.

A reaction temperature of 244 ca and the base is preferably 5 to 80° C.,more preferably 10 to 60° C., and further preferably 15 to 50° C. fromthe viewpoint of reaction activity and the selectivity of 1233 yd. Whenthe reaction temperature does not reach the above-described range, thereis a possibility of a decrease in a reaction rate and the reactionyield, and when unreacted 244 ca remains excessively, separation from1233 yd is likely to be difficult. Further, when the reactiontemperature exceeds the above-described range, there are a possibilityof an increase in a production amount of 1-chloro-3,3-difluoropropyne tobe produced by further dehydrofluorination of 1233 yd and a possibilityof a decrease in the selectivity of 1233 yd.

When the unreacted 244 ca remains, it is also possible to concentrate244 ca by distillation and recycle it as the raw material of the presentinvention.

1233 yd to be obtained in the manufacturing method of the presentinvention may be an E-isomer, a Z-isomer, or a mixture of these. Here, aboiling point of 244 ca is 53° C., a boiling point of 1233 yd(Z) is 54°C., and a boiling point of 1233 yd(E) is 47 to 48° C.

In the manufacturing method of the present invention, the reaction of244 ca and the base causes the dehydrofluorination reaction (de-HFreaction) of 244 ca. In order to involve the base in the reaction, it isrequired to be physically in contact with 244 ca. When the manufacturingmethod of the present invention is performed by the gas phase reaction,a method of bringing the base in a solid, preferably, powder state and244 ca in a gaseous state into contact with each other can be cited.

When the manufacturing method of the present invention is performed bythe liquid phase reaction, a method of bringing the base dissolved in asolvent, namely, the base in a solution state and 244 ca in a liquidstate into contact with each other, or the like can be cited. In these,from the viewpoint of the reaction time, the reaction yield, and theselectivity of 1233 yd, the latter liquid phase reaction is preferable.For example, a solution obtained by dissolving the base in the solventand 244 ca are preferably brought into contact with each other by usinga means such as stirring. The case of performing the manufacturingmethod of the present invention by the liquid phase reaction ispreferable from the viewpoint that a reactor with a smaller size can beemployed compared with the gas phase reaction.

As long as the solvent which can be used when the manufacturing methodof the present invention is performed by the liquid phase reaction, andis used for preparing the base in the solution state is a solvent whichis capable of dissolving a predetermined amount of the base and does notcontribute to the dehydrofluorination reaction, it is not particularlylimited. For example, as the solvent, water is preferable from theviewpoint of being capable of dissolving the alkali metal hydroxidesufficiently, having no side reaction derived from the solvent, and thelike.

When the manufacturing method of the present invention is performed bythe liquid phase reaction, it is preferably performed by a method inwhich 244 ca and the base such as the alkali metal hydroxide aresubjected to the liquid phase reaction in the presence of the solvent.

In an amount of the base, in terms of the reaction rate, a proportion(unit %) of mass of the base such as the alkali metal hydroxide to atotal amount (mass) of the solvent and the base is preferably an amountof 0.5 to 48 mass %, and more preferably 20 to 40 mass %. When the baseamount is below the above-described range, a sufficient reaction ratecannot be sometimes obtained. On the other hand, when the base amountexceeds the above-described range, there is a possibility that theproduction amount of 1-chloro-3,3-difluoropropyne to be produced by afurther dehydrofluorination reaction of 1233 yd increases and theselectivity of 1233 yd decreases.

When the manufacturing method of the present invention is performed asthe liquid phase reaction, for the purpose of accelerating the reactionmore, another substance which does not impair the effect of the presentinvention may be made to exist in a reaction system. For example, whenas a base solution, the base solution is used by using a solvent with ahigh hydrophilic property, as the other substance, a phase-transfercatalyst, a water-soluble organic solvent capable of dissolving 244 ca,or the like is preferably made to exist, and the phase-transfer catalystis particularly preferable.

As the phase-transfer catalyst, there can be cited a quaternary ammoniumsalt, a quaternary phosphonium salt, a quaternary arsonium salt, asulfonium salt, crown ether, or the like, and the quaternary ammoniumsalt is preferable.

When the phase-transfer catalyst is the quaternary ammonium salt, acompound (hereinafter, sometimes referred to as “compound (i)”)represented by the following formula (i) can be cited.

Where, in the formula (i), R¹¹ to R¹⁴ each independently represent amonovalent hydrocarbon group or a monovalent hydrocarbon group to whicha functional group inert to a reaction is bonded, and Y⁻ represents ananion.

When R¹¹ to R¹⁴ are each the hydrocarbon group, there can be cited analkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,an aryl group, or the like, and the alkyl group or the aryl group ispreferable. The number of carbon atoms of R¹¹ to R¹⁴ is preferably 4 to100. R¹¹ to R¹⁴ may be each the same group or may be groups differentfrom one another. A functional group when R¹¹ to R¹⁴ are each themonovalent hydrocarbon group to which a functional group inert to areaction is bonded is appropriately selected depending on reactionconditions, but there can be cited a halogen atom, an alkoxycarbonylgroup, an acyloxy group, a nitrile group, an acyl group, a carboxylgroup, an alkoxyl group, or the like.

As R¹¹R¹²R¹³R¹⁴N⁺, N there can be cited tetramethylammonium,tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium,methyltri-n-octylammonium, cetyltrimethylammonium,benzyltrimethylammonium, benzyltriethylammonium,cetylbenzyldimethylammonium, cetylpyridinium, n-dodecylpyridinium,phenyltrimethylammonium, phenyltriethylammonium, N-benzylpicolinium,pentamethonium, hexamethonium, or the like.

As Y⁻, there can be cited a chlorine ion, a fluorine ion, a bromide ion,an iodine ion, a sulfate ion, a nitrate ion, a phosphate ion, aperchlorate ion, a hydrogen sulfate ion, a hydroxide ion, an acetateion, a benzoate ion, a benzenesulfonate ion, a p-toluenesulfonate ion,or the like, and the chlorine ion, the bromide ion, the iodine ion, thehydrogen sulfate ion, or the hydroxide ion is preferable.

As the compound (i), from the viewpoint of general versatility andreactivity, combinations of the below-described R¹¹R¹²R¹³R¹⁴N⁺ and thebelow-described Y⁻ are preferable.

R¹¹R¹²R¹³R¹⁴N⁺: tetramethylammonium, tetraethylammonium,tetra-n-propylammonium, tetra-n-butylammonium, ormethyltri-n-octylammonium.

Y⁻: a fluorine ion, a chlorine ion, a bromide ion, an iodine ion, or ahydroxide ion.

As the quaternary ammonium salt, tetra-n-butylammonium chloride (TBAC),tetra-n-butylammonium bromide (TBAB), or methyltri-n-octylammoniumchloride (TOMAC) is preferable.

When the phase-transfer catalyst is the quaternary phosphonium salt, acompound represented by the following formula (ii) can be cited.

Where, in the formula (ii), R²¹ to R²⁴ each independently represent amonovalent hydrocarbon group, and Y⁻ represents an anion.

As the hydrocarbon group in each of R²¹ to R²⁴, there can be cited analkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,an aryl group, or the like, and the alkyl group or the aryl group ispreferable.

As quaternary phosphonium (R²¹R²²R²³R²⁴P⁺) in the formula (ii), therecan be cited tetraethylphosphonium, tetra-n-butylphosphonium,ethyltri-n-octylphosphonium, cetyltriethylphosphonium,cetyltri-n-butylphosphonium, n-butyltriphenylphosphonium,n-amyltriphenylphosphonium, methyltriphenylphosphonium,benzyltriphenylphosphonium, tetraphenylphosphonium, or the like.

As Y⁻, there can be cited a chlorine ion, a fluorine ion, a bromide ion,an iodine ion, a sulfate ion, a nitrate ion, a phosphate ion, aperchlorate ion, a hydrogen sulfate ion, a hydroxide ion, an acetateion, a benzoate ion, a benzenesulfonate ion, a p-toluenesulfonate ion,or the like, and the fluorine ion, the chlorine ion, or the bromide ionis preferable.

When the phase-transfer catalyst is the quaternary arsonium salt, acompound represented by the following formula (iii) can be cited.

Where, in the formula (iii), R³¹ to R³⁴ each independently represent amonovalent hydrocarbon group, and Y⁻ represents an anion.

As the hydrocarbon group in each of R³¹ to R³⁴, for example, there canbe cited an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an aryl group, or the like, and the alkyl group orthe aryl group is preferable.

As Y⁻, a halogen ion is preferable, and a fluorine ion, a chlorine ion,or a bromide ion is more preferable.

As the quaternary arsonium salt represented by the formula (iii), therecan be cited triphenylmethylarsonium fluoride, tetraphenylarsoniumfluoride, triphenylmethylarsonium chloride, tetraphenylarsoniumchloride, tetraphenylarsonium bromide, or the like. As the quaternaryarsonium salt, triphenylmethylarsonium chloride is particularlypreferable.

When the phase-transfer catalyst is the sulfonium salt, a compoundrepresented by the following formula (iv) can be cited.

Where, in the formula (iv), R⁴¹ to R⁴³ each independently represent amonovalent hydrocarbon group, and Y⁻ represents an anion.

As the hydrocarbon group in each of R⁴¹ to R⁴³, for example, there canbe cited an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an aryl group, or the like, and the alkyl group orthe aryl group is preferable.

As Y⁻, a halogen ion is preferable, and a fluorine ion, a chlorine ion,or a bromide ion is more preferable.

As the sulfonium salt represented by the formula (iv), there can becited di-n-butylmethylsulfonium iodide, tri-n-butylsulfoniumtetrafluoroborate, dihexylmethylsulfonium iodide,dicyclohexylmethylsulfonium iodide, dodecylmethylethylsulfoniumchloride, tris(diethylamino)sulfonium difluorotrimethylsilicate, or thelike. As the sulfonium salt, dodecylmethylethylsulfonium chloride isparticularly preferable.

As the crown ether, there can be cited 18-crown-6, dibenzo-18-crown-6,dicyclohexyl-18-crown-6, or the like.

An amount of the phase-transfer catalyst is preferably 0.001 to 5 partsby mass and more preferably 0.01 to 1 parts by mass with respect to 100parts by mass of 244 ca. When the amount of the phase-transfer catalystis too small, a sufficient reaction rate cannot be sometimes obtained,and even though a large amount thereof is used, a reaction acceleratingeffect according to the use amount thereof cannot be obtained, which isdisadvantageous to a cost aspect.

Further, when the reaction system separates into an aqueous phase and anorganic phase, the organic phase and the aqueous phase including thebase may be compatibilized by making the water-soluble organic solvent(for example, tetraglyme or the like) exist in the reaction systeminstead of the phase-transfer catalyst, or the phase-transfer catalystand the water-soluble organic solvent may be used in combination.

As the water-soluble organic solvent, a solvent which is an organicsolvent capable of dissolving 244 ca and has no effect on the reactionof the present invention is preferable, and tetraethylene glycoldimethyl ether (tetraglyme), sulfolane, t-butanol, or the like ispreferable. The water-soluble solvent usually has compatibility with thebase solution.

An amount of the water-soluble organic solvent is preferably 1 to 200parts by mass and more preferably 10 to 100 parts by mass with respectto 100 parts by mass of 244 ca. When the amount of the water-solubleorganic solvent is below the above-described range, a sufficientreaction rate cannot be sometimes obtained. Further, when the amount ofthe water-soluble organic solvent exceeds the above-described range, abase concentration becomes low, and therefore a reaction rate becomessmall and a reaction accelerating effect according to the use amountcannot be obtained.

When the phase-transfer catalyst or the water-soluble organic solvent isused, after introduction into a reactor, it is preferable to bring thecompounds involved in the reaction and these sufficiently in contactwith each other by a commonly-used agitator.

The reaction in the present invention may be performed in a batch mode,or may be performed in a semi-continuous mode or a continuous flow mode.The reaction time can be appropriately regulated depending on each ofthe modes. As long as a material of the reactor is a material which isinert to reaction solution components including 244 ca, thephase-transfer catalyst, the water-soluble organic solvent, the base,the solvent for making this into the solution, and the reaction product,and the like and has corrosion resistance, it is not particularlylimited. For example, there can be cited glass, iron, nickel, an alloysuch as stainless steel containing iron or the like as a main component,and the like.

In the reaction of the present invention, 1233 yd is produced by thedehydrofluorination reaction of 244 ca, and production of3-chloro-1,1,2-trifluoropropene (1233 yc) is also considered. However,when the manufacturing method of the present invention is performed bythe liquid phase reaction, particularly when it is performed by using anaqueous solution of the alkali metal hydroxide as the base, there is theadvantage that 1233 yc is hardly produced and 1233 yd can be selectivelyobtained.

When the manufacturing method of the present invention is performed bythe liquid phase reaction, a reaction solution is left as it is after areaction completion, thereby separating it into an organic phase and anaqueous phase. In the organic phase, other than 1233 yd which is anobject, unreacted 244 ca, 1-chloro-3,3-difluoropropyne to be produced byfurther dehydrofluorination of 1233 yd, and the like can be included. Inrecovering 1233 yd from the organic phase including these, a separationand purification method by ordinary distillation or the like ispreferably employed. Here, when 1233 yd(Z) is included in a product, theboiling points of 244 ca and 1233 yd(Z) are close to each other, andtherefore it is preferable to perform highly accurate distillation.Further, separation of an E-isomer and a Z-isomer of 1233 yd may beperformed by the separation and purification method such as thedistillation in order to increase a yield of 1233 yd(Z).

By recovering 1233 yd obtained by the manufacturing method of thepresent invention by the separation and purification as described above,purified 1233 yd containing 1233 yd at a high purity can be obtained.When the purified 1233 yd obtained in such a manner includes acidcontent such as HCl, water, or oxygen, there is the possibility ofcorrosion of equipment in using it, a decrease in stability of 1233 yd,or the like. Accordingly, the acid content, namely, a content of thechlorine ion and the fluorine ion is preferably less than 10 mass ppm,more preferably less than 1 mass ppm, and most preferably less than 0.1mass ppm with respect to a total amount of the purified 1233 yd.Further, a moisture concentration in the purified 1233 yd is preferablyless than 1000 mass ppm, and most preferably less than 100 mass ppm. Anoxygen concentration in the purified 1233 yd is preferably 1000 mass ppmor less, and more preferably 500 mass ppm or less. When theabove-described ranges are beyond them, there is a possibility thatdecomposition of 1233 yd occurs or degreasing-cleaning ability isinhibited.

According to the manufacturing method of the present invention,performing the reaction without using special operation and reactiondevice by using 244 ca which can be easily obtained and stably suppliedmakes it possible to manufacture 1233 yd at a high reaction rate andwith a high selectivity. Moreover, when the reaction by themanufacturing method of the present invention is performed by the liquidphase reaction, it is possible to reduce the reactor size in a case ofmanufacturing the same amount of 1233 yd compared with the gas phasereaction. That is, according to the present invention, it is possible todrastically reduce a cost required for the raw material andmanufacturing facilities.

EXAMPLES

Hereinafter, the present invention will be specifically explained byexamples, but the present invention is not limited by these examples.

[Condition of Gas Chromatography]

In production of the following various compounds, a chemical compositionanalysis of an obtained reaction composition was performed by using agas chromatography (GC). DB-1301 (60 m in length×250 μm in insidediameter×1 μm in thickness, manufactured by Agilent Technologies, Inc.)was used as a column.

Production Example 1 of 244 ca

244 ca was produced by the following method. The following method is amethod of obtaining 244 ca by chlorinating TFPO with thionyl chloride asillustrated in the formula (2).

<Synthesis of 244 ca>

In a two-liter four-necked flask with an agitator, a Dimroth condenser,and a glass distillation column (a measured value of five stages in thenumber of stages) packed with Raschig ring, 1204 g (9.12 mol) of TFPOand 12 g (0.17 mol) of N,N-dimethylformamide (DMF) were added. Intothere, 1078 g (0.12 mol) of thionyl chloride was dropped and stirred atroom temperature for 12 hours. Thereafter, a reactor was heated to 100°C., and reactive distillation was performed at a ratio of 5/1 of refluxtime/distillation time by using a reflux timer. Distilled 244 ca wasneutralized by a 20 mass % aqueous potassium hydroxide solution.Recovered 244 ca (purity 100%) was 979 g (6.50 mol).

Example 1

In a two-liter four-necked flask with an agitator and a Dimrothcondenser, 989.40 g of 244 ca obtained in Production Example 1 and 9.89g of tetra-n-butylammonium chloride (TBAC) were put, and the flask washeated to 50° C. A reaction temperature was maintained at 50° C., and1396.01 g of a 40 mass % aqueous potassium hydroxide (KOH) solution wasdropped over 30 minutes. Thereafter, stirring was continued for 52hours, and an organic layer was recovered. Note that the reaction timein this example is a total time of a time required for theabove-described dropping and a time of performing the stirring after thedropping, namely, 52.5 hours.

After water washing the recovered organic layer, an analysis using thegas chromatography was carried out. The result is indicated in Table 1.

The conversion ratio described below indicates a proportion (unit: %) ofa molar amount of a material (unless otherwise stated, 244 ca) consumedby the reaction to a molar amount of a material (244 ca) used for thereaction, and the selectivity means a proportion (unit: %) of aproduction amount (molar amount) of each of products (1233 yd(E), 1233yd(Z), and 1-chloro-3,3-difluoropropyne) to a total amount of theproducts.

The yield (%) of 1233 yd(E) or 1233 yd(Z) is a numeric value in which amolar amount of products (1233 yd(E) and 1233 yd(Z)) recovered from anorganic phase obtained by the reaction is indicated by a proportion(unit: %) to the molar amount of 244 ca introduced into a reactionsystem. “HCFO-1233 yd(E, Z) yield (%)” presented in Table 1 presents atotal of yields of 1233 yd(E) and 1233 yd(Z) (other tables are alsosimilar).

After water washing the organic layer recovered in the above, purified1233 yd including 1233 yd(E) and 1233 yd(Z) was obtained bydistillation. In the purified 1233 yd, a chlorine ion concentration was0.14 mass ppm, a fluorine ion concentration was 0.16 mass ppm, amoisture concentration was 230 mass ppm, and an oxygen concentration was400 ppm.

Examples 2 to 9

In the reaction device in Example 1, reactions were each performed in aprocess similar to that in Example 1 except to change the reactor to athree-necked or four-necked flask with an arbitrary capacity and furtherchange reaction conditions to conditions presented in Table 1 or Table2.

Table 1 or Table 2 presents results of a chemical composition analysisby a gas chromatogram of an organic layer obtained in each of theexamples together with the conditions of the reaction and so on. Notethat reaction times presented in Table 1 and Table 2 were each indicatedin a unit of hour (h) obtained by rounding off a unit of minute (min).

Example 10

In the reaction device in Example 1, a reaction was performed in aprocess similar to that in Example 1 except to change the reactor to anautoclave made of SUS and having a capacity of 25 mL in which a pressuremeter was placed and change reaction conditions to the conditionspresented in Table 2. Table 2 presents a result of a chemicalcomposition analysis by a gas chromatogram of an organic layer obtainedin Example 10 together with the conditions of the reaction and so on.

Example 11

In the reaction device in Example 1, a reaction was performed in aprocess similar to that in Example 1 except to change the reactor to anautoclave made of Hastelloy and having a capacity of 1 L in which thepressure meter was placed and change reaction conditions to theconditions presented in Table 2. Table 2 presents a result of a chemicalcomposition analysis by a gas chromatogram of an organic layer obtainedin Example 11 together with the conditions of the reaction and so on.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 ReactionHCFC-244ca input 989.40 961.96 10.02 9.98 10.21 condition amount (g)Type of phase-transfer TBAC TBAC TBAC TOMAC TBAC catalyst Phase-transfercatalyst 1 1 1 1 1 use amount (Parts by mass with respect to 100 partsby mass of HCFC-244ca) Reaction temperature (° C.) 50 15 5 50 50 Type ofbase KOH KOH KOH KOH KOH Base concentration (mass %) 40 40 40 40 20 inaqueous base solution Aqueous base solution 30 30 5 5 5 dropping time(min) Aqueous base solution 1396.01 1340.11 9.85 10.25 10.49 inputamount (g) Molar amount of base 1.50 1.50 1.05 1.10 0.55 with respect to1 mol of HCFC-244ca Reaction time (h) 53 62 62 38 50 Reaction GC Type ofRaw Reaction Raw Reaction Raw Reaction Raw Reaction Raw Reaction crudeanalysis compound material product material product material productmaterial product material product solution result HCFC-244ca 100.00 2.05100.00 10.12 100.00 97.56 100.00 8.51 100.00 61.29 composition [mass %]HCFO-1233yd(E) 0.00 8.37 0.00 7.66 0.00 0.21 0.00 5.13 0.00 3.04HCFO-1233yd(Z) 0.00 89.43 0.00 82.20 0.00 2.23 0.00 86.26 0.00 35.611-chloro-3,3- 0.00 0.14 0.00 0.01 0.00 0.00 0.00 0.11 0.00 0.05difluoropropyne Organic phase recovered 850.2 889.4 9.8 9.2 9.2 amount(g) HCFC-244ca 98.2 90.6 4.8 92.1 44.7 conversion ratio (%)HCFO-1233yd(E) 8.5 8.5 8.5 5.6 7.9 selectivity (%) HCFO-1233yd(Z) 91.391.5 91.4 94.3 92.0 selectivity (%) 1-chloro-3,3-difluoropropyne 0.1 0.00.0 0.1 0.1 selectivity (%) HCFO-1233yd (E, Z) 96.9 95.8 2.7 97.4 40.3yield (%)

TABLE 2 Example 6 Example 7 Example 8 Example 9 Reaction HCFC-244cainput 9.78 10.17 9.93 251.31 condition amount (g) Type of phase-transferTBAC TBAC TBAC TBAB catalyst Phase-transfer catalyst 1 1 1 1 use amount(Parts by mass with respect to 100 parts by mass of HCFC-244ca) Reactiontemperature (° C.) 50 50 50 50 Type of base KOH NaOH K₂CO₃ KOH Baseconcentration (mass %) 40 40 20 34 in aqueous base solution Aqueous basesolution 5 5 5 5 dropping time (min) Aqueous base solution 27.30 14.9349.97 631.55 input amount (g) Molar amount of base 2.99 1.10 1.10 2.29with respect to 1 mol of HCFC-244ca Reaction time (h) 50 50 50 30Reaction GC Type of Raw Reaction Raw Reaction Raw Reaction Raw Reactioncrude analysis compound material product material product materialproduct material product solution result HCFC-244ca 100.00 0.06 100.005.89 100.00 84.38 100.00 0.02 composition [mass %] HCFO-1233yd(E) 0.008.56 0.00 7.61 0.00 1.28 0.00 8.92 HCFO-1233yd(Z) 0.00 91.25 0.00 86.380.00 14.34 0.00 91.02 1-chloro-3,3- difluoro propyne 0.00 0.13 0.00 0.120.00 0.00 0.00 0.04 Organic phase recovered amount (g) 8.3 9.0 9.8 214.2HCFC-244ca conversion 99.9 94.8 16.4 100.0 ratio (%) HCFO-1233yd(E) 8.68.1 8.2 8.9 selectivity (%) HCFO-1233yd(Z) 91.3 91.8 91.8 91.0selectivity (%) 1-chloro-3,3-difluoropropyne 0.1 0.1 0.0 0.0 selectivity(%) HCFO-1233yd (E, Z) 97.7 95.9 17.9 98.3 yield (%) Example 10 Example11 Reaction HCFC-244ca input 9.28 246.06 condition amount (g) Type ofphase-transfer TBAC TBAB catalyst Phase-transfer catalyst 1 1 use amount(Parts by mass with respect to 100 parts by mass of HCFC-244ca) Reactiontemperature (° C.) 70 50 Type of base KOH KOH Base concentration (mass%) 40 40 in aqueous base solution Aqueous base solution 5 5 droppingtime (min) Aqueous base solution 16.14 530.46 input amount (g) Molaramount of base 1.87 2.31 with respect to 1 mol of HCFC-244ca Reactiontime (h) 88 30 Reaction GC Type of Raw Reaction Raw Reaction crudeanalysis compound material product material product solution resultHCFC-244ca 100.00 0.09 100.00 0.01 composition [mass %] HCFO-1233yd(E)0.00 9.31 0.00 9.00 HCFO-1233yd(Z) 0.00 86.98 0.00 90.84 1-chloro-3,3-difluoro propyne 0.00 3.61 0.00 0.15 Organic phase recovered amount (g)4.3 202.9 HCFC-244ca conversion 100.0 100.0 ratio (%) HCFO-1233yd(E) 9.59.0 selectivity (%) HCFO-1233yd(Z) 88.8 90.8 selectivity (%)1-chloro-3,3-difluoropropyne 3.7 0.1 selectivity (%) HCFO-1233yd (E, Z)51.3 94.9 yield (%)

Examples 12 to 15

In Examples 12 to 15, in the reaction device in Example 1, the reactorwas changed to the three-necked or four-necked flask with an arbitrarycapacity, and water-soluble organic solvents were each used instead ofusing TBAC which was a phase-transfer catalyst. Reactions were eachperformed in a process similar to that in Example 1 except to change atype and an input amount of each of the used water-soluble organicsolvents and reaction conditions other than them to conditions presentedin Table 3. Table 3 presents results of a chemical composition analysisby a gas chromatogram of an organic layer obtained in each of theexamples together with the conditions of the reaction and so on.

TABLE 3 Example 12 Example 13 Example 14 Example 15 Reaction HCFC-244cainput amount (g) 10.05 10.01 10.27 10.25 condition Type of water-solubleorganic solvent Tetraethylene Tetraethylene Sulfolane t-butanol glycolglycol dimethyl ether dimethyl ether Water-soluble organic solvent useamount 50 100 100 100 (Parts by mass with respect to 100 parts by massof HCFC-244ca) Reaction temperature (° C.) 50 50 50 50 Type of base KOHKOH KOH KOH Base concentration (mass %) in aqueous 40 40 40 40 basesolution Aqueous base solution dropping time (min) 5 5 5 5 Aqueous basesolution input amount (g) 10.42 10.90 10.80 10.78 Molar amount of basewith respect to 1.11 1.17 1.13 1.13 1 mol of HCFC-244ca Reaction time(h) 30 30 30 30 Reaction GC Type of compound Raw Reaction Raw ReactionRaw Reaction Raw Reaction crude analysis material product materialproduct material product material product solution result HCFC-244ca100.00 72.85 100.00 68.86 100.00 31.71 100.00 35.68 composition [mass %]HCFO-1233yd(E) 0.00 2.23 0.00 2.83 0.00 5.61 0.00 0.19 HCFO-1233yd(Z)0.00 24.91 0.00 28.29 0.00 62.67 0.00 64.12 1-chloro-3,3-difluoropropyne0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 Organic phase recovered amount(g) 9.9 9.9 10.2 10.1 HCFC-244ca conversion ratio (%) 28.4 31.8 68.664.7 HCFO-1233yd(E) selectivity (%) 8.2 9.1 8.2 0.3 HCFO-1233yd(Z)selectivity (%) 91.8 90.9 91.8 99.7 1-chloro-3,3-difluoropropyneselectivity (%) 0.0 0.0 0.0 0.0 HCFO-1233yd (E, Z) yield (%) 30.8 35.677.9 73.3

Comparative Example 1

An insertion tube (material: SUS316, diameter: 3 mm) was introduced intothe center of a vertical fixed-bed reactor (material: SUS316, 22.0 mm ininside diameter×200 mm in height), a K-type thermocouple was insertedtherein, and an internal temperature was measured. The center portion ofthe reactor was filled with 83.0 mL (43.0 g) of an activated carbon(manufactured by Japan EnviroChemicals, Limited, SHIRASAGI activatedcarbon CMX), which was set as a catalyst layer. The catalyst layer washeated to 100° C. and dried by an electric furnace while supplyingnitrogen gas at 300 mL/min. A raw material preheating mixing lineconnecting a gas feed line and a raw material supply line and heated to70° C. was connected to an upper portion of the reactor.

Nitrogen, whose gas flow rate was regulated by using a mass flowcontroller, was supplied from the gas feed line to the raw materialpreheating mixing line. 244 ca which was a raw material, whose liquidflow rate was regulated by using a plunger pump, was supplied throughthe raw material supply line to the raw material preheating mixing lineheated to 70° C. A product was continuously taken out of a lower portionof the reactor. Part of the product taken out of the lower portion ofthe reactor was picked, and a chemical composition analysis wasperformed by the gas chromatography (GC). Hereinafter, the product takenout of the lower portion of the reactor is referred to as an outlet gas.

Nitrogen and the raw material were introduced into the reactor underconditions presented in Table 4 and made to react with each othercontinuously for three hours. Part of the outlet gas was pickedimmediately before a reaction completion, and the chemical compositionanalysis was performed by the gas chromatography (GC). Table 4 presentsa result.

Comparative Examples 2 to 4

A vertical fixed-bed reactor (material: SUS316, 22.6 mm in insidediameter×200 mm in height) was used as a reactor and alumina(manufactured by JGC Catalysts and Chemicals Ltd., N612N) was used as acatalyst, and the catalyst was dried at 300° C. in a process similar tothat in Comparative Example 1. Thereafter, chlorodifluoromethane(HFC-22) was supplied at 300 mL/min, and the catalyst was activated forabout ten hours until a composition of the outlet gas was stabilized.Reactions were each performed in a process similar to that inComparative Example 1 except to change a reaction temperature andreaction conditions other than it to conditions presented in Table 4.Table 4 presents the reaction conditions and results.

TABLE 4 Comparative Comparative Comparative Comparative Example 1Example 2 Example 3 Example 4 Reaction Catalyst Activated carbon Al₂O₃Al₂O₃ Al₂O₃ condition Reaction temperature (° C.) 350.0 350.0 450.0500.0 Reaction pressure (MPa (gage)) 0 0 0 0 Contact time (sec) 20 20 2020 Linear velocity (cm/sec) 1 1 1 1 N₂ flow rate (Nml/min) 49.0 52.045.0 42.0 244ca flow rate (Nml/min) 49.0 52.0 45.0 42.0 Reaction GC Typeof compound Raw Reaction Raw Reaction Raw Reaction Raw Reaction crudeanalysis material product material product material product materialproduct solution result HCFC-244ca 100.000 99.211 99.911 98.800 99.91194.900 99.911 97.924 composition [mass %] HCFO-1233yd(E) 0.000 0.0300.000 0.000 0.000 0.000 0.000 0.000 HCFO-1233yd(Z) 0.000 0.125 0.0000.016 0.000 0.016 0.000 0.016 1-chloro-3,3- 0.000 0.000 0.000 0.0300.000 0.069 0.000 0.022 difluoropropyne Others 0.000 0.635 0.089 1.1540.089 5.015 0.089 2.037 HCFC-244ca conversion ratio (%) 0.79 1.11 5.021.99 HCFO-1233yd(E) selectivity (%) 0.04 0.00 0.00 0.00 HCFO-1233yd(Z)selectivity (%) 0.16 0.05 0.02 0.03 1-chloro-3,3-difluoropropyne 0.003.71 7.34 3.17 selectivity (%) HCFO-1233yd (E, Z) yield (%) 0.04 0.0010.001 0.0005

What is claimed is:
 1. A method of manufacturing1-chloro-2,3,3-trifluoropropene, comprising; subjecting3-chloro-1,1,2,2-tetrafluoropropane to a dehydrofluorination reaction ina liquid phase in the presence of a base and a solvent, and a proportionof mass of the base to a total mass of the solvent and the base is 0.5to 40 mass %.
 2. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 1, wherein the baseis at least one selected from the group consisting of a metal hydroxide,a metal oxide, and a metal carbonate.
 3. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 1, wherein the baseis a metal hydroxide.
 4. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 1, wherein the baseis at least one selected from the group consisting of potassiumhydroxide and sodium hydroxide.
 5. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 1, wherein an amountof the base is 0.5 to 10.0 mol with respect to 1 mol of the3-chloro-1,1,2,2-tetrafluoropropane.
 6. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 1, wherein thedehydrofluorination reaction is performed at a reaction temperature of 5to 80° C.
 7. The method of manufacturing 1-chloro-2,3,3-trifluoropropeneaccording to claim 1, wherein the solvent is water.
 8. The method ofmanufacturing 1-chloro-2,3,3-trifluoropropene according to claim 1,wherein the dehydrofluorination reaction is performed in the presence ofa phase-transfer catalyst.
 9. The method of manufacturing1-chloro-2,3,3-trifluoropropene according to claim 8, wherein thephase-transfer catalyst is a quaternary ammonium salt.
 10. The method ofmanufacturing 1-chloro-2,3,3-trifluoropropene according to claim 9,wherein the quaternary ammonium salt is at least one selected from thegroup consisting of tetra-n-butylammonium chloride,tetra-n-butylammonium bromide, and methyltri-n-octylammonium chloride.11. The method of manufacturing 1-chloro-2,3,3-trifluoropropeneaccording to claim 1, wherein the dehydrofluorination reaction isperformed in the presence of a water-soluble organic solvent capable ofdissolving the 3-chloro-1,1,2,2-tetrafluoropropane.
 12. The method ofmanufacturing 1-chloro-2,3,3-trifluoropropene according to claim 11,wherein the water-soluble organic solvent is used in a proportion of 1to 200 parts by mass to 100 parts by mass of the3-chloro-1,1,2,2-tetrafluoropropane.
 13. The method of manufacturing1-chloro-2,3,3-trilluoropropene according to claim 1, wherein thedehydrofluorination reaction is conducted for a time of 62 hours orless.
 14. The method of manufacturing 1-chloro-2,3,3-trifluoropropeneaccording to claim 1, wherein the dehydrofluorination reaction isperformed at a reaction temperature of 5 to 60° C.